Formylated alklbenzenesulfonyl halide compound and process for preparing the same

ABSTRACT

A formylated alkylbenzenesulfonyl halide compound represented by the following general formula (I): ##STR1## wherein R 1  is an alkyl group having 1 to 5 carbon atoms; R 2  and R 3  are each a member selected from the group consisting of a hydrogen atom and alkyl groups having 1 to 5 carbon atoms; X is a halogen atom; the sulfonyl halide group is present at the ortho or para position while the formyl group at the para or ortho position relative to the group R 1  when R 2  and R 3  are both a hydrogen atom, while the sulfonyl halide group and the formyl group are present at the para positions relative to the groups R 1  and R 2 , respectively, when R 2  is an alkyl group and R 3  is a hydrogen atom, or the sulfonylhalide group and the formyl group are present at the para positions relative to the groups R 1  and R 2 , respectively, when R 2  and R 3  are both an alkyl group; the compound (I) being prepared by reacting an alkylbenzene represented by the following formula (III) with carbon monoxide and a halosulfonic acid represented by the following formula (II) in the presence of an antimony halide: ##STR2## wherein all of X in the formula (II) and R 1 , R 2  and R 3  in the formula (III) are as defined above.

This is a division, of application Ser. No. 384,386 filed July 25, 1989,now U.S. Pat. No. 5,030,752.

BACKGROUND OF THE INVENTION

The present invention relates to a novel formylated alkylbenzenesulfonylhalide compound and a process for preparing the same. More particularly,the invention relates to a novel formylated alkylbenzenesulfonyl halidecompound having a benzene ring substituted with a sulfonyl halide groupand a formyl group at the ortho and para positions thereof,respectively, relative to an alkyl group, or at the para positionsthereof relative to two alkyl groups, and a process for preparing thesame under atmospheric pressure at ordinary temperature in one step.

Aromatic sulfonyl compounds are industrially important as intermediatesfor the syntheses of drugs, dyes, etc. and starting materials for thepreparation of transparent polysulfone resins having a high heatresistance.

Methods of introducing a sulfonyl group into an aromatic compoundinclude one as disclosed in Japanese patent application Kokaipublication No. 59-141556 wherein chlorobenzene is reacted withchlorosulfonic acid to synthesize 4-chlorobenzenesulfonyl chloride.

Meanwhile, methods of introducing a formyl group into an alkylbenzeneinclude one as disclosed in Japanese patent publication No. 39-29760wherein an alkylbenzene is reacted with carbon monoxide in the presenceof hydrogen fluoride and boron trifluoride.

However, there are no known methods of introducing a sulfonyl group anda formyl group simultaneously into an aromatic compound.

SUMMARY OF THE INVENTION

A first object of the present invention is to provide a novel formylatedalkylbenzenesulfonyl halide compound having a benzene ring substitutedwith a sulfonyl halide group and a formyl group at the ortho and parapositions thereof, respectively, relative to an alkyl group, or at thepara positions thereof relative to two alkyl groups.

A second object of the present invention is to provide a process forpreparing a formylated alkylbenzenesulfonyl halide compound of the kindas described above under atmospheric pressure at ordinary temperature inone step.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The novel formylated alkylbenzenesulfonyl halide compound of the presentinvention is represented by the following general formula (I): ##STR3##wherein R₁ is an alkyl group having 1 to 5 carbon atoms; R₂ and R₃ areeach a member selected from the group consisting of a hydrogen atom andalkyl groups having 1 to 5 carbon atoms; X is a halogen atom; thesulfonyl halide group is present at the ortho or para position while theformyl group at the para or ortho position relative to the group R₁ whenR₂ and R₃ are both a hydrogen atom, while the sulfonyl halide group andthe formyl group are present at the para positions relative to thegroups R₁ and R₂, respectively, when R₂ is an alkyl group and R₃ is ahydrogen atom, or the sulfonyl halide group and the formyl group arepresent at the para positions relative to the groups R₁ and R₂,respectively, when R₂ and R₃ are both an alkyl group.

Specific examples of the novel formylated alkylbenzenesulfonyl halidecompound of the present invention include the following compoundsenumerated under the respective compound No.

(1) 3-formyl-6-methylbenzenesulfonyl fluoride ##STR4##

(2) 3-formyl-4-methylbenzenesulfonyl fluoride ##STR5##

(3) 3-formyl-4,6-dimethylbenzenesulfonyl fluoride ##STR6##

(4) 3-formyl-4,6-diethylbenzenesulfonyl fluoride ##STR7##

(5) 2-formyl-4,5-dimethylbenzenesulfonyl fluoride ##STR8##

(6) 2-formyl-4,5-diethylbenzenesulfonyl fluoride ##STR9##

(7) 3-formyl-2,4,6-trimethylbenzenesulfonyl fluoride ##STR10##

(8) 3-formyl-2,4,6-triethylbenzenesulfonyl fluoride ##STR11##

(9) 3-formyl-6-n-pentylbenzenesulfonyl fluoride ##STR12##

(10) 3-formyl-4,6-dimethylbenzenesulfonyl chloride ##STR13##

The novel compound of the present invention can be prepared by reactingan alkylbenzene represented by the following general formula (III) withcarbon monoxide and a halosulfonic acid represented by the followinggeneral formula (II) in the presence of an antimony halide catalyst:

    XSO.sub.3 H

wherein X is a halogen atom, and ##STR14## wherein R₁ is an alkyl grouphaving 1 to 5 carbon atoms, and R₂ and R₃ are each a member selectedfrom the group consisting of a hydrogen atom and alkyl groups having 1to 5 carbon atoms.

When a halosulfonic acid is mixed with an antimony halide, a superacid,such as [FSO₂ ⁺ ]+[OH--]SbF₅, is formed. The acid strength of such asuperacid is at least 100 times as high as that of 100% sulfuric acid.Therefore, the use of the superacid makes it possible to carry outreactions which cannot proceed in systems wherein sulfuric acid orpolyphosphoric acid is used. Specifically, formyl cations [CHO⁺ ] andsulfonyl cations [SO₂ X⁺ ] can be present stably in the superacid to beavailable for electrophilic attack on an aromatic compound to facilitatethe occurrence of electrophilic substitution reactions thereof with thearomatic compound.

More specifically, sulfonyl cations and formyl cations attack the orthoand para positions, respectively, or two para positions, if present, ofan alkylbenzene. One example of such reaction processes will be shown inthe following reaction formula: ##STR15##

Thus, according to the process of the present invention, bothsulfonation and carbonylation proceed readily and simultaneously merelyby adding an alkylbenzene slowly to a mixture of a halosulfonic acidwith an antimony halide in an atmosphere of carbon monoxide. After thecompletion of the reaction, the reaction mixture is poured into icewater and extracted with an organic solvent to give the desiredformylated alkylbenzenesulfonyl halide in one step.

In the case of alkylbenzenes of the formula (III) wherein R₂ and R₃ areboth a hydrogen atom, namely monoalkylbenzenes, compounds havingsulfonyl halide and formyl groups introduced thereinto at the ortho andpara positions relative to the alkyl group thereof, such as theaforementioned compounds Nos. 1, 2 and 9 are obtained by the process ofthe present invention.

Dialkylbenzenes of the formula (III) wherein R₂ is an alkyl group whileR₃ is a hydrogen atom are classified into ones having the two alkylgroups at the meta positions relative to each other, and ones having thetwo alkyl groups at the ortho positions relative to each other. Forexample, the aforementioned compounds Nos. 3, 4 and 10 are obtained fromthe former type of dialkylbenzenes, while, for example, theaforementioned compounds Nos. 5 and 6 are obtained from the latter typeof dialkylbenzenes.

In the case of trialkylbenzenes of the formula (III) wherein R₂ and R₃are both an alkyl group, for example the aforementioned compounds Nos. 7and 8 are obtained.

Specific examples of the alkylbenzene to be used in the presentinvention include monoalkylbenzenes such as toluene, ethylbenzene,butylbenzene, pentylbenzene, isopropylbenzene, and isobutylbenzene;1,3-dialkylbenzenes such as m-xylene, 1,3-diethylbenzene,1-ethyl-3-methylbenzene, 1,3-dibutylbenzene, and 1,3-dipentylbenzene;1,2-dialkylbenzenes such as o-xylene, 1,2-diethylbenzene,1,2-dipropylbenzene, and 1,2-dipentylbenzene; and 1,3,5-trialkylbenzenessuch as 1,3,5-trimethylbenzene and 1,3,5-triethylbenzene.

Fluorosulfonic acid, chlorsulfonic acid, etc. are usable as thehalosulfonic acid, while antimony pentafluoride, antimony pentachloride,etc. are usable as the antimony halide.

The molar ratio of the starting materials to the catalyst is such thatalkylbenzene : halosulfonic acid : antimony halide=1:[0.2˜10]:[0.2˜5].

Mere replacement of the air in a reactor with carbon monoxide willsuffice to provide the atmosphere of carbon monoxide, and it is notalways necessary to blow carbon monoxide into a reaction mixture or topressurize the reactor with carbon monoxide.

Ordinary temperature will suffice as the reaction temperature, though itmay be raised up to 60° C. The reaction time ranges from about 2 toabout 24 hours.

Since the viscosity of the reaction mixture increases in keeping withthe progress of the reaction, it is preferable to use a solvent such astrifluoroacetic acid, trichloroacetic acid, dichloroacetic acid,sulfuric acid or acetic anhydride, the use of which permits the reactionto proceed smoothly.

The resulting product was subjected to NMR, IR and mass spectrometricanalyses to confirm that it is a novel compound.

As described hereinbefore, all of the formylated alkylbenzenesulfonylhalide compounds according to the present invention are novel compounds.These compounds are useful as starting materials of drugs, dyes,engineering plastics, etc.

Further, according to the process of the present invention, a formylgroup and a sulfonyl group can be simultaneously introduced into analkylbenzene molecule under atmospheric pressure at ordinary temperatureto give the desired compound in one step.

The following Examples will illustrate the present invention in moredetail.

EXAMPLE 1 Preparation of 3-formyl-6-methylbenzenesulfonyl fluoride(compound No. 1) and 3-formyl-4-methylbenzenesulfonyl fluoride (compoundNo. 2)

A three-necked flask connected with a carbon monoxide gas buret ispurged with carbon monoxide through the buret and charged with 20 ml offluorosulfonic acid, 10 ml of antimony pentafluoride and 10.6 ml oftoluene. The reaction was effected under stirring at 25° C. for 8 hours.The molar ratio of toluene : fluorosulfuric acid : antimonypentafluoride was 1 : 3.5 : 1.4, while the consumption of carbonmonoxide was 2.24 l.

After the completion of the reaction, the reaction mixture was pouredinto ice water and extracted with benzene, which was then removed fromthe extract. The remaining oily substance was subjected to gaschromatographic, NMR, IR, and mass spectrometric analyses to confirm theformation of 3.03 g of 3-formyl-6-methylbenzenesulfonyl fluoride(compound No. 1) in a yield of 15 % based on toluene.

The physical properties of the compound No. 1 are as follows:

mass spectrum: M⁺ (m/e)=202

¹ H NMR chemical shift δ (CCl₄): 2.74 (1H, d) 7.50 (1H, s) 8.00 (1H, d)8.30 (1H, s) 9.88 (1H, s)

IR spectrum (cm⁻¹): 1715, 1600, 1420, 1220, 770.

It was also confirmed through the analyses that isomeric3-formyl-4-methylbenzenesulfonyl fluoride (compound No. 2) was formed ina yield of 5 % based on toluene.

The physical properties of the compound No. 2 are as follows:

mass spectrum: M+(m/e)=202

¹ H NMR chemical shift δ (CCl₄): 2.78 (3H, s), 7.45 (1H, d) 7.95 (1H,d), 8.22 (1H, s) 10 20 (1H, s)

IR spectrum (cm⁻¹): 1700, 1600, 1410, 1180, 1220.

EXAMPLE 2 Preparation of 3-formyl-4,6-dimethylbenzenesulfonyl fluoride(compound No. 3)

A three-necked flask purged with carbon monoxide in the same manner asthat of Example 1 was charged with 20 ml of fluorosulfonic acid, 10 mlof antimony pentafluoride, and trifluoroacetic acid as a solvent, towhich 12.2 ml of m-xylene was slowly added at 25° C. The reaction waseffected under stirring at 25° C. for 6 hours. The molar ratio ofm-xylene : fluorosulfonic acid : antimony pentafluoride was 1 : 3.5 :1.4, while the consumption of carbon monoxide was 2.23 l. The reactionmixture was treated in the same manner as that of Example 1 to give anoily product, which was then subjected to the same analyses as those ofExample 1 to confirm the formation of3-formyl-4,6-dimethylbenzenesulfonyl fluoride (compound No. 3) in ayield of 83 % based on m-xylene. The physical properties of the compoundNo. 3 are as follows:

mass spectrum: M⁺ (m/e)=216

¹ H NMR chemical shift δ (CDCl₃): 2.71 (3H, s) 2.74 (3H, s) 7.35 (1H, s)8.41 (1H, s) 10.23 (1H, s)

¹³ C NMR chemical shift δ (CDCl₃) 19.6, 20.4, 131.1, 133.6, 134.0,136.6, 143.4, 148.1, 189.9

IR spectrum (cm⁻¹): 1690, 1600, 1410, 1380, 1260, 1180, 770, 650.

Melting point: 68.5°˜70° C.

EXAMPLE 3 Preparation of 3-formyl-4,6-diethylbenzenesulfonyl fluoride(compound No. 4)

12.48 ml of 1,3-diethylbenzene was reacted with 20 ml of fluorosulfonicacid in a carbon monoxide atmosphere in the presence of 10 ml ofantimony pentafluoride under stirring at 25° C. for 8 hours insubstantially the same manner as that of Example 1. The molar ratio of1,3-diethylbenzene : fluorosulfonic acid : antimony pentafluoride was 1: 4.4 : 1.7, while the consumption of carbon monoxide was 1,800 ml. Thereaction product was extracted in the same manner as that of Example 1and then subjected to the same analyses as those of Example 1 to confirmthe formation of 11.8 g of 3-formyl-4,6-diethylbenzenesulfonyl fluoride(compound No. 4) in a yield of 60 % based on 1,3-diethylbenzene.

mass spectrum: M⁺ (m/e)=244

¹ H NMR chemical shift δ (CCl₄) 10.05 (1H, s) 8.23 (1H, s) 7.31 (1H, s)3.11 (2H, q) 3.03 (2H, q) 1.33 (3H, t) 1.28 (3H, t)

IR spectrum (cm⁻¹): 2980, 1700, 1600, 1410, 1210, 765.

EXAMPLE 4 Preparation of 2-formyl-4,5-dimethylbenzenesulfonyl fluoride(compound No. 5)

7.2 ml of o-xylene was reacted with 20 ml of fluorosulfonic acid in acarbon monoxide atmosphere in the presence of 10 ml of antimonypentafluoride under stirring at 25° C. for 8 hours in substantially thesame manner as that of Example 1. The molar ratio of o-xylene :fluorosulfonic acid : antimony pentafluoride was 1 : 5.9 : 2.37, whilethe consumption of carbon monoxide was 1,340 ml. The reaction productwas extracted in the same manner as that of Example 1 and then subjectedto the same analyses as those of Example to confirm the formation of 2.6g of 2-formyl-4,5-dimethylbenzenesulfonyl fluoride (compound No. 5) in ayield of 20 % based on o-xylene.

mass spectrum: M⁺ (m/e)=216

¹ H NMR chemical shift δ (CCl₄): 2.70 (6H, s) 8.00 (1H, s) 8.35 (1H, s)10.09 (1H, s)

IR spectrum (cm⁻¹): 1700, 1600, 1420, 1210, 770.

EXAMPLE 5 Preparation of 2-formyl-4,5-diethylbenzenesulfonyl fluoride(compound No. 6)

7.7 ml of 1,2-diethylbenzene was reacted with 20 ml of fluorosulfonicacid and carbon monoxide in the presence of 12.6 ml of antimonypentafluoride and 10 ml of chloroacetic acid as a solvent at 25° C. for8 hours in substantially the same manner as that of Example 1. The molarratio of 1,2-diethylbenzene : fluorosulfonic acid : antimonypentafluoride was 1 : 7 : 2, while the consumption of carbon monoxidewas 1,120 ml. The reaction product was extracted in the same manner asthat of Example 1 and then subjected to the same analyses as those ofExample 1 to confirm the formation of 1.2 g of2-formyl-4,5-diethylbenzenesulfonyl fluoride (compound No. 6) in a yieldof 10 % based on 1,2-diethylbenzene.

mass spectrum: M⁺ (m/e)=244

¹ H NMR chemical shift δ (CCl₄): 1.25 (6H, t) 2.40˜3.3 (4H, m) 7.0 (1H,s) 7.8 (1H, s) 10.0 (1H, s)

IR spectrum (cm⁻¹): 2980, 1700, 1600, 1210.

EXAMPLE 6 Preparation of 3-formyl-2,4,6-trimethylbenzenesuffonylfluoride (compound No. 7)

18.9 ml of 1,3,5-trimethylbenzene was reacted with 20 ml offluorosulfonic acid and carbon monoxide in the presence of 10 ml ofantimony pentafluoride and 10 ml of trifluoroacetic acid as a solvent at20° C. for 48 hours in substantially the same manner as that ofExample 1. The molar ratio of 1,3,5-trimethylbenzene : fluorosulfonicacid : antimony pentafluoride was 1 : 3.5 : 1.4, while the consumptionof carbon monoxide was 2.24 l. The same analyses as those of Example 1were made to confirm the formation of 6.9 g of3-formyl-2,4-6-trimethylbenzenesulfonyl fluoride (compound No. 7) in ayield of 30 % based on 1,3,5-trimethylbenzene.

mass spectrum: M⁺ (m/e)=230

¹ H NMR chemical shift δ (CDl₃): 2.50 (3H, s), 2.65 (3H, s) 2.71 (3H,s), 6.95 (1H, s) 10.58 (1H, s)

IR spectrum (cm⁻¹): 3000, 1700, 1590, 1400, 1205, 760.

EXAMPLE 7 Preparation of 3-formyl-2,4,6-triethylbenzenesulfonyl fluoride(compound No. 8)

9.3 ml of 1,3,5-triethylbenzene was reacted with 20 ml of fluorosulfonicacid and carbon monoxide in the presence of 10 ml of antimonypentafluoride at 35° C. for 8 hours in substantially the same manner asthat of Example 1. The molar ratio of 1,3,5-triethylbenzene :fluorosulfonic acid : antimony pentafluoride was 1 : 7 : 2.8, while theconsumption of carbon monoxide was 1.13 l. The same analyses as those ofExample 1 were made to confirm the formation of 1.36 g of3-formyl-2,4-6-triethylbenzenesulfonyl fluoride (compound No. 8) in ayield of 10 % based on 1,3,5-triethylbenzene.

mass spectrum: M⁺ (m/e)=272

¹ H NMR chemical shift δ (CCl₄): 1.3 (9H, m), 2.0 (6H, m), 7.4 (1H, s)10.1 (1H, s)

IR spectrum (cm⁻¹): 1700, 1410, 1200.

EXAMPLE 8 Preparation of 3-formyl-6-n-pentylbenzenesulfonyl fluoride(compound No. 9)

8.6 ml of n-pentylbenzene was reacted with 20 ml of fluorosulfonic acidand carbon monoxide in the presence of 10 ml of antimony pentafluorideat 35° C. for 8 hours in substantially the same manner as that ofExample 1. The molar ratio of n-pentylbenzene : fluorosulfonic acid :antimony pentafluoride was 1 : 7.0 : 2.8, while the consumption ofcarbon monoxide was 450 ml. The same analyses as those of Example 1 weremade to confirm the formation of 1.36 g of3-formyl-6-n-pentylbenzenesulfonyl fluoride (compound No. 9) in a yieldof 10 % based on n-pentylbenzene.

mass spectrum: M⁺ (m/e)=258

¹ H NMR chemical shift δ (CCl₄): 1.2 (3H, t), 1.7 (4H, m), 2.6 (4H, m),7.0˜8.0 (3H, m), 9.9 (1H, s)

IR spectrum (cm⁻¹): 1710, 1410, 1220.

EXAMPLE 9 Preparation of 3-formyl-4,6-dimethylbenzenesulfonyl chloride(compound No. 10)

6.1 ml of m-xylene was reacted with 20 ml of chlorosulfonic acid andcarbon monoxide in the presence of 10 ml of antimony pentafluoride at30° C. for 10 hours in substantially the same manner as that ofExample 1. The molar ratio of m-xylene : chlorosulfonic acid : antimonypentafluoride was 1 : 6.2 : 2.8, while the consumption of carbonmonoxide was 900 ml. The same analyses as those of Example 1 were madeto confirm the formation of 0.6 g of3-formyl-4,6-dimethylbenzenesulfonyl chloride (compound No. 10) in ayield of 5% based on m-xylene.

mass spectrum: M⁺ (m/e)=232

IR spectrum (cm⁻¹): 1710, 1410, 1200, 700.

What is claimed is:
 1. A process for preparing a formylatedalkylbenzenesulfonyl halide compound represented by the followinggeneral formula (I), comprising reacting an alkylbenzene represented bythe following general formula (III) with carbon monoxide and ahalosulfonic acid represented by the following general formula (II) inthe presence of an antimony halide: ##STR16## wherein, in the formulae(I) and (II), X is a halogen atom;in the formula (I), R₁ is an alkylgroup having 1 to 5 carbon atoms; R₂ and R₃ are each a member selectedfrom the group consisting of a hydrogen atom and alkyl groups having 1to 5 carbon atoms; the sulfonyl halide group is present at the ortho orpara position while the formyl group at the para or ortho positionrelative to said group R₁ when R₂ and R₃ are both a hydrogen atom, whilethe sulfonyl halide group and the formyl group are present at the parapositions relative to said groups R₁ and R₂, respectively, when R₂ is analkyl group and R₃ is a hydrogen atom, or the sulfonyl halide group andthe formyl group are present at the para positions relative to saidgroups R₁ and R₂, respectively, when R₂ and R₃ are both an alkyl group;and in the formula (III), R₁ is an alkyl group having 1 to 5 carbonatoms, R₂ and R₃ are each a member selected from the group consisting ofa hydrogen atom and alkyl groups having 1 to 5 carbon atoms.
 2. Theprocess as claimed in claim 1, wherein said alkylbenzene is a memberselected from the group consisting of monoalkylbenzenes,1,2-dialkylbenzenes, 1,3-dialkylbenzenes, and 1,3,5-trialkylbenzenes. 3.The process as claimed in claim 1, wherein X is a member selected fromthe group consisting of a fluorine atom and a chlorine atom.